Macroscopic and high-throughput printing of aligned nanostructured polymer semiconductors for MHz large-area electronics

High-mobility semiconducting polymers offer the opportunity to develop flexible and large-area electronics for several applications, including wearable, portable and distributed sensors, monitoring and actuating devices. An enabler of this technology is a scalable printing process achieving uniform electrical performances over large area. As opposed to the deposition of highly crystalline films, orientational alignment of polymer chains, albeit commonly achieved by non-scalable/slow bulk alignment schemes, is a more robust approach towards large-area electronics. By combining pre-aggregating solvents for formulating the semiconductor and by adopting a room temperature wired bar-coating technique, here we demonstrate the fast deposition of submonolayers and nanostructured films of a model electron-transporting polymer. Our approach enables directional self-assembling of polymer chains exhibiting large transport anisotropy and a mobility up to 6.4 cm2 V−1 s−1, allowing very simple device architectures to operate at 3.3 MHz. Thus, the proposed deposition strategy is exceptionally promising for mass manufacturing of high-performance polymer circuits.

[1]  Arthur A. Tracton.  Coatings Technology Handbook , 2005 .

[2]  Stephen R. Forrest,et al.  The path to ubiquitous and low-cost organic electronic appliances on plastic , 2004, Nature.

[3]  S. Fabiano,et al.  From Monolayer to Multilayer N‐Channel Polymeric Field‐Effect Transistors with Precise Conformational Order , 2012, Advanced materials.

[4]  M. Antognazza,et al.  Mapping orientational order of charge-probed domains in a semiconducting polymer. , 2014, ACS nano.

[5]  Henning Sirringhaus,et al.  Microstructure of polycrystalline PBTTT films: domain mapping and structure formation. , 2012, ACS nano.

[6]  M. Toney,et al.  Effect of Backbone Regioregularity on the Structure and Orientation of a Donor–Acceptor Semiconducting Copolymer , 2014 .

[7]  Vivek Subramanian,et al.  High‐Performance Printed Transistors Realized Using Femtoliter Gravure‐Printed Sub‐10 μm Metallic Nanoparticle Patterns and Highly Uniform Polymer Dielectric and Semiconductor Layers , 2012, Advanced materials.

[8]  C. McNeill,et al.  Structure–Function Relationships of High-Electron Mobility Naphthalene Diimide Copolymers Prepared Via Direct Arylation , 2014 .

[9]  A. Facchetti,et al.  Aggregation in a high-mobility n-type low-bandgap copolymer with implications on semicrystalline morphology. , 2012, Journal of the American Chemical Society.

[10]  H. Sirringhaus.  25th Anniversary Article: Organic Field-Effect Transistors: The Path Beyond Amorphous Silicon , 2014, Advanced materials.

[11]  Yong-Young Noh,et al.  Frequency operation of low-voltage, solution-processed organic field-effect transistors , 2011 .

[12]  K. Müllen,et al.  Microstructure evolution and device performance in solution-processed polymeric field-effect transistors: the key role of the first monolayer. , 2012, Journal of the American Chemical Society.

[13]  M. Halik,et al.  Low‐Voltage Self‐Assembled Monolayer Field‐Effect Transistors on Flexible Substrates , 2013, Advanced materials.

[14]  S. Patil,et al.  Diketopyrrolopyrrole-diketopyrrolopyrrole-based conjugated copolymer for high-mobility organic field-effect transistors. , 2012, Journal of the American Chemical Society.

[15]  Florian S. U. Fischer,et al.  Anisotropic Charge Transport in Spherulitic Poly(3‐hexylthiophene) Films , 2012, Advanced materials.

[16]  Barbara Stadlober,et al.  Self‐Aligned Megahertz Organic Transistors Solution‐Processed on Plastic , 2015 .

[17]  Takao Someya,et al.  Contact resistance and megahertz operation of aggressively scaled organic transistors. , 2012, Small.

[18]  Keith A. Nugent,et al.  SRI 2009, 10TH INTERNATIONAL CONFERENCE ON RADIATION INSTRUMENTATION , 2010 .

[19]  Juhwan Kim,et al.  Simple Bar‐Coating Process for Large‐Area, High‐Performance Organic Field‐Effect Transistors and Ambipolar Complementary Integrated Circuits , 2013, Advanced materials.

[20]  Donal D. C. Bradley,et al.  Polymer Field‐Effect Transistors Fabricated by the Sequential Gravure Printing of Polythiophene, Two Insulator Layers, and a Metal Ink Gate , 2010 .

[21]  Yong-Young Noh,et al.  Fully-printed, all-polymer, bendable and highly transparent complementary logic circuits , 2015 .

[22]  Haydyn D. T. Mertens,et al.  A low-background-intensity focusing small-angle X-ray scattering undulator beamline , 2013 .

[23]  M. Brinkmann,et al.  Orienting semi-conducting π-conjugated polymers. , 2014, Macromolecular rapid communications.

[24]  M. Toney,et al.  A general relationship between disorder, aggregation and charge transport in conjugated polymers. , 2013, Nature materials.

[25]  C. McNeill,et al.  Observation of a distinct surface molecular orientation in films of a high mobility conjugated polymer. , 2013, Journal of the American Chemical Society.

[26]  Jan Fyenbo,et al.  Product integration of compact roll-to-roll processed polymer solar cell modules: methods and manufacture using flexographic printing, slot-die coating and rotary screen printing , 2010 .

[27]  Yun‐Hi Kim,et al.  Dramatic Inversion of Charge Polarity in Diketopyrrolopyrrole‐Based Organic Field‐Effect Transistors via a Simple Nitrile Group Substitution , 2014, Advanced materials.

[28]  Yong-Young Noh,et al.  High speeds complementary integrated circuits fabricated with all‐printed polymeric semiconductors , 2011 .

[29]  Henning Sirringhaus,et al.  Critical role of alkyl chain branching of organic semiconductors in enabling solution-processed N-channel organic thin-film transistors with mobility of up to 3.50 cm² V(-1) s(-1). , 2013, Journal of the American Chemical Society.

[30]  Liyan Yu,et al.  Wire-bar coating of semiconducting polythiophene / insulating polyethylene blend thin films for organic transistors. , 2011 .

[31]  Zhihua Chen,et al.  Naphthalenedicarboximide- vs perylenedicarboximide-based copolymers. Synthesis and semiconducting properties in bottom-gate N-channel organic transistors. , 2009, Journal of the American Chemical Society.

[32]  Henning Sirringhaus,et al.  High‐Performance Ambipolar Diketopyrrolopyrrole‐Thieno[3,2‐b]thiophene Copolymer Field‐Effect Transistors with Balanced Hole and Electron Mobilities , 2012, Advanced materials.

[33]  Yong-Young Noh,et al.  Toward Printed Integrated Circuits based on Unipolar or Ambipolar Polymer Semiconductors , 2013, Advanced materials.

[34]  Florian S. U. Fischer,et al.  Charge Transport Anisotropy in Highly Oriented Thin Films of the Acceptor Polymer P(NDI2OD‐T2) , 2014 .

[35]  Luigino Criante,et al.  Control of charge transport in a semiconducting copolymer by solvent-induced long-range order , 2013, Scientific Reports.

[36]  A. Heeger,et al.  General strategy for self-assembly of highly oriented nanocrystalline semiconducting polymers with high mobility. , 2014, Nano letters.

[37]  Marco Sampietro,et al.  All‐Organic and Fully‐Printed Semitransparent Photodetectors Based on Narrow Bandgap Conjugated Molecules , 2014, Advanced materials.

[38]  Mario Caironi,et al.  High-resolution direct-writing of metallic electrodes on flexible substrates for high performance organic field effect transistors , 2013 .

[39]  A. Kawai,et al.  Characterization of SiO2 Surface Treated by HMDS Vapor and O2 plasma with AFM Tip , 2003 .

[40]  Y. Arakawa,et al.  Current-gain cutoff frequencies above 10 MHz for organic thin-film transistors with high mobility and low parasitic capacitance , 2009 .

[41]  J. N. Burghartz,et al.  S-Parameter Characterization of Submicrometer Low-Voltage Organic Thin-Film Transistors , 2013, IEEE Electron Device Letters.

[42]  Chao Jiang,et al.  Novel top-contact monolayer pentacene-based thin-film transistor for ammonia gas detection. , 2014, ACS applied materials & interfaces.

[43]  A. Facchetti,et al.  A high-mobility electron-transporting polymer for printed transistors , 2009, Nature.

[44]  Bin Sun,et al.  Record High Electron Mobility of 6.3 cm2V−1s−1 Achieved for Polymer Semiconductors Using a New Building Block , 2014, Advanced materials.

[45]  M. Antognazza,et al.  Sub‐Micrometer Charge Modulation Microscopy of a High Mobility Polymeric n‐Channel Field‐Effect Transistor , 2011, Advanced materials.

[46]  M. Caironi,et al.  Nature of Charge Carriers in a High Electron Mobility Naphthalenediimide Based Semiconducting Copolymer , 2014 .

[47]  Vivek Subramanian,et al.  Megahertz-class printed high mobility organic thin-film transistors and inverters on plastic using attoliter-scale high-speed gravure-printed sub-5 μm gate electrodes , 2014 .

[48]  Hung Phan,et al.  High‐Mobility Field‐Effect Transistors Fabricated with Macroscopic Aligned Semiconducting Polymers , 2014, Advanced materials.

[49]  K. Müllen,et al.  Nanofiber growth and alignment in solution processed n-type naphthalene-diimide-based polymeric field-effect transistors , 2012 .

[50]  Zhihua Chen,et al.  Remarkable order of a high-performance polymer. , 2013, Nano letters.

[51]  Zhihua Chen,et al.  Orientation-dependent electronic structures and charge transport mechanisms in ultrathin polymeric n-channel field-effect transistors. , 2013, ACS applied materials & interfaces.

[52]  M. Brinkmann,et al.  Large Scale Alignment and Charge Transport Anisotropy of pBTTT Films Oriented by High Temperature Rubbing , 2013 .

[53]  Yong‐Young Noh,et al.  Solution-processed barium salts as charge injection layers for high performance N-channel organic field-effect transistors. , 2014, ACS applied materials & interfaces.

[54]  M Sampietro,et al.  Fully Inkjet‐Printed Organic Photodetectors with High Quantum Yield , 2013, Advanced materials.

[55]  M. Toney,et al.  Highly oriented crystals at the buried interface in polythiophene thin-film transistors , 2006 .

[56]  Wei Jiang,et al.  High Mobility, Air Stable, Organic Single Crystal Transistors of an n‐Type Diperylene Bisimide , 2012, Advanced materials.

[57]  Peter Strohriegl,et al.  N‐Type Self‐Assembled Monolayer Field‐Effect Transistors and Complementary Inverters , 2013 .

[58]  Byeong Kwon Ju,et al.  Organic Thin-Film Transistors with Short Channel Length Fabricated by Reverse Offset Printing , 2011 .

[59]  Yong-Young Noh,et al.  Downscaling of self-aligned, all-printed polymer thin-film transistors. , 2007, Nature nanotechnology.

[60]  Gui Yu,et al.  A stable solution-processed polymer semiconductor with record high-mobility for printed transistors , 2012, Scientific Reports.

[61]  Juhwan Kim,et al.  Organic integrated circuits for information storage based on ambipolar polymers and charge injection engineering , 2014 .

[62]  H. Sirringhaus,et al.  A Selenophene‐Based Low‐Bandgap Donor–Acceptor Polymer Leading to Fast Ambipolar Logic , 2012, Advanced materials.

[63]  Lifeng Chi,et al.  High Performance Field‐Effect Ammonia Sensors Based on a Structured Ultrathin Organic Semiconductor Film , 2013, Advanced materials.

[64]  F. Krebs,et al.  Roll‐to‐Roll fabrication of large area functional organic materials , 2013 .

[65]  R. L. Elsenbaumer,et al.  Handbook of conducting polymers , 1986 .

[66]  Hao Wang,et al.  Solution‐Processable, Low‐Voltage, and High‐Performance Monolayer Field‐Effect Transistors with Aqueous Stability and High Sensitivity , 2015, Advanced materials.

[67]  H. Sirringhaus,et al.  Very Low Degree of Energetic Disorder as the Origin of High Mobility in an n‐channel Polymer Semiconductor , 2011 .